Calorimetric study of the thermodynamic properties of Mn 5 O 8

Pinghui Zhang, Jue Liu, Katharine Page, Alexandra Navrotsky

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Manganese oxides occur widely in nature and have technical applications in various areas. This study quantitatively evaluates the thermodynamic properties of Mn 5 O 8 , a binary manganese oxide that has a layered structure and contains coexisting divalent and tetravalent manganese. Three samples of the Mn 5 O 8 phase with slightly different manganese average oxidation states (Mn AOS) were synthesized using a wet chemical method and annealing. Synchrotron X-ray analysis revealed that the samples contain a small amount of a secondary MnO 2 phase that cannot be identified using laboratory X-ray diffraction. High-temperature oxide melt solution calorimetry in molten sodium molybdate at 700°C showed that all three samples are slightly higher in enthalpy than an isochemical mixture of bixbyite (Mn 2 O 3 ) and pyrolusite (MnO 2 ), probably rendering them metastable in free energy with respect to isochemical mixtures of bixbyite and pyrolusite. However, the energetic metastability (endothermic enthalpy) of Mn 5 O 8 is very small (<6 kJ/mol) and does not depend significantly on the Mn AOS. Thus, although Mn 5 O 8 probably does not appear on the equilibrium Mn-O phase diagram, its small metastability allows its synthesis by a variety of low temperature reactions.

Original languageEnglish (US)
Pages (from-to)1394-1401
Number of pages8
JournalJournal of the American Ceramic Society
Volume102
Issue number3
DOIs
StatePublished - Mar 2019

ASJC Scopus subject areas

  • Ceramics and Composites
  • Materials Chemistry

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